JP5030780B2 - Damping emulsion - Google Patents

Description

The present invention relates to an emulsion for vibration damping materials. More specifically, the present invention relates to an emulsion for a damping material that is useful as a material for a damping material that is used to prevent vibration and noise in various structures and maintain silence.

The damping material is for keeping vibration and noise in various structures and keeping quiet, for example, in addition to being used under the indoor floor of an automobile, a railway vehicle, a ship, an aircraft, an electrical device, Widely used in building structures and construction equipment. As a material used for such a damping material, conventionally, a molded product such as a plate-shaped molded body or a sheet-shaped molded body made of a material having vibration absorption performance and sound absorption performance has been used. If the shape of the sound generation location is complicated, it is difficult to apply these molded products to the vibration generation location. Various methods have been studied. That is, for example, asphalt sheets containing inorganic powder have been used under the interior floor of automobiles, etc. However, since there is a need to heat-seal, improvement in workability and the like is desired, and vibration suppression is desired. Various damping material compositions and polymers forming the material have been studied.

Thus, as an alternative material for such molded products, coating-type damping materials (paints) have been developed. For example, a coating film formed by spraying or spraying a corresponding portion by an arbitrary method. Thus, various vibration-damping paints that can obtain a vibration absorption effect and a sound absorption effect have been proposed. Specifically, for example, as a water-based vibration-damping paint with improved coating film hardness obtained by blending a synthetic resin powder with a color developing agent such as asphalt, rubber, synthetic resin, and the like suitable for indoor use in automobiles, Anti-vibration coatings in which activated carbon is dispersed as a filler in a resin emulsion have been developed. However, even with these conventional products, the vibration damping performance is still not at a sufficiently satisfactory level, and there is a need for a technique that can further exhibit the vibration damping performance.

By the way, in order for the coating film to act as a damping material, it is necessary to have a certain film thickness, but when drying a thick coating film, it tends to dry from the surface, While the internal coating still retains moisture, the coating near the surface can be cured. For this reason, evaporation of moisture inside the coating film may cause the coating film in the vicinity of the already hardened surface to expand to the outside of the coating film or cause cracks in the coating film. Since the characteristics as a vibration material are not sufficiently expressed, the significance of forming a coating film for use as a vibration damping material is lost. In particular, when a coating film is formed using an emulsion paint, the emulsion paint tends to fuse and form a film as soon as the amount of water around the particles decreases, so these problems become significant. Therefore, there is a demand for a technique for improving this point and obtaining an industrially useful vibration damping material.

With respect to a conventional material for damping material, a thickener for aqueous damping material made of a polymer having an alkali-soluble monomer unit and an associative monomer unit has been disclosed (for example, see Patent Document 1). The paint blended with this thickening agent for water-based vibration damping materials is excellent in dryness and can sufficiently prevent cracks and expansion on the surface, giving a high-quality vibration damping material with excellent vibration damping properties. It is possible to make it industrially useful. However, there has been room for improvement in order to further improve physical properties such as vibration damping properties, drying properties, and mechanical stability, and to make them more suitable as materials used for vibration damping materials of various structures.
JP 2004-137485 A (page 2)

The present invention has been made in view of the above-described present situation, and is excellent in vibration damping properties, drying properties and mechanical stability in a wide temperature range, and can improve the skinning property of the coating film surface. It aims at providing the emulsion for materials.

The inventors of the present invention have made various studies on the emulsion for vibration damping materials. When an emulsion produced using an anionic emulsifier is used, the stability is improved due to the balance of hydrophobic group-hydrophilic group in the structure of the anionic emulsifier. It has been found that an effect is exerted in the application, and further, by specifying the type of anionic emulsifier and the amount of the anionic emulsifier used, it can be found that an emulsion for a vibration damping material including an emulsion having a somewhat large particle diameter can be obtained. As a result, the mechanical stability and pigment dispersibility are significantly improved, and it has excellent vibration damping and drying properties over a wide temperature range, and it can improve the surface of the coating film as a vibration damping material. I found what I could do and came up with the idea that I could solve the above problems. And it discovered that such emulsion for damping materials became a useful thing especially as a material of the damping material of various structures, and reached | attained this invention.
In addition, the emulsion for vibration damping materials of the present invention can be suitably used particularly for water-based coating type vibration damping materials.

That is, the present invention is a damping material emulsion comprising an emulsion produced using an anionic emulsifier, wherein the anionic emulsifier comprises polyoxyethylene alkyl ether sulfate, alkyl diphenyl ether disulfonate and alkenyl. The amount of the anionic emulsifier used is at least one selected from the group consisting of succinic acid di-salts, with respect to 100 parts by weight of the total amount of monomer components used in the production of the emulsion. It is an emulsion for damping material that is 0 part by weight or more.
The present invention is described in detail below.

The emulsion for vibration damping material of the present invention (also referred to as “emulsion for vibration damping material (I)”) includes an emulsion (also referred to as “emulsion (i)”) produced using an anionic emulsifier. The emulsion may be produced using other emulsifiers such as nonionic emulsifiers as long as an anionic emulsifier is used in the production. Moreover, 1 type (s) or 2 or more types can be used for an emulsion. Moreover, unless the effect of this invention is impaired, you may further contain the other component.
In such a damping material emulsion (I), the amount of the anionic emulsifier used is 1.0 part by weight or more with respect to 100 parts by weight of the total amount of monomer components used in the production of the emulsion (i). It is appropriate that When the amount is less than 1.0 part by weight, excellent drying properties cannot be exhibited, and there is a possibility that the pigment miscibility when mixed with the pigment may not be sufficient. There is a possibility that it cannot be useful. Preferably it is 1.5 weight part or more, More preferably, it is 2.0 weight part or more.

The emulsion for vibration damping materials of the present invention further comprises at least one anionic emulsifier selected from the group consisting of polyoxyethylene alkyl ether sulfate, alkyl diphenyl ether disulfonate, and alkenyl succinate. The content of the anionic emulsifier is preferably 1.0 part by weight or more with respect to 100 parts by weight of the total amount of monomer components used in the production of the emulsion.
Thus, in addition to the emulsion produced using the anionic emulsifier, the emulsion for the vibration damping material further contains a specific amount of the specific anionic emulsifier, and the effect of the emulsion for the vibration damping material of the present invention is as follows. It will be more effective.
The content of the anionic emulsifier in the emulsion for vibration damping materials is preferably 3.0 parts by weight or more, more preferably 4.0 parts by weight or more. In consideration of economy, it is preferably 6.0 parts by weight or less.

The content of the anionic emulsifier does not include the amount of the anionic emulsifier consumed by reacting with the monomer component or the like during the production of the emulsion (i). That is, the content of the anionic emulsifier means the content of a free anionic emulsifier. As a method for quantifying the free anionic emulsifier, for example, it can be carried out as follows.
(Quantitative method of free anionic emulsifier)
After adding and stirring 150 ml of methanol to 15 g of emulsion (I) for damping material, the mixture is centrifuged at 80,000 rpm × 20 minutes at room temperature using an ultra-high speed centrifuge. After confirming that the emulsion for damping material (I) is separated into the upper layer (supernatant liquid) / lower layer (resin sedimentation layer), collect the upper supernatant liquid as much as possible and dry it at 110 ° C for 2 hours. And measure the remaining mass. Since the component dissolved in the supernatant (transparent) is presumed to be an emulsifier, the content of the emulsifier can be determined from the mass of the residue.

The anionic emulsifier is suitably at least one selected from the group consisting of polyoxyethylene alkyl ether sulfate, alkyl diphenyl ether disulfonate and alkenyl succinate. Of these, at least one selected from the group consisting of polyoxyethylene alkyl ether sulfates and alkyl diphenyl ether disulfonates is preferred. The polyoxyethylene alkyl ether sulfate ester salt is particularly preferably a polyoxyethylene alkyl ether sulfate ester salt to which an ethylene oxide (EO) chain having 7 or more units is added. A form that is at least one selected from the group consisting of polyoxyethylene alkyl ether sulfates having an ethylene oxide chain of 7 or more units added thereto and alkyl diphenyl ether disulfonates is also included in the present invention. One preferred form. Thereby, it becomes possible to fully exhibit the effect of this invention. The hydrophobic group of the polyoxyethylene alkyl ether sulfate ester salt is not particularly limited. For example, lauryl group, octylphenyl group, nonylphenyl group, polycyclic phenyl group, stearyl group, oleyl group, higher alkyl group, cetyl 1 type (s) or 2 or more types, such as a group and a myristyl group, are suitable.
A preferable use range of the anionic emulsifier is 2% or more, more preferably 2.5% or more.
Particularly suitable compounds of the anionic emulsifier include, for example, Newcol 723SF (EO mole number = 23) (manufactured by Nippon Emulsifier Co., Ltd.); Latem E-118B (EO mole number = 20), Latemul E-150 (EO mole) Number = 50), Perex SS-H (sodium alkyldiphenyl ether disulfonate) (all trade names, manufactured by Kao Corporation), New Coal 707SF, New Coal 707SF (EO mole number = 7; manufactured by Nippon Emulsifier Co., Ltd.), New Coal 714SF (EO mole number = 14; manufactured by Nippon Emulsifier Co., Ltd.), Haitenol NF-08 (EO mole number = 8; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

In the present invention, other commonly used anionic emulsifiers can be used in combination with at least one of the anionic emulsifiers described above. Such an anionic emulsifier is not particularly limited, and examples thereof include alkyl sulfate salts such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium alkyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; sulfonated paraffin salt and the like. Alkyl sulfonates such as sodium dodecylbenzene sulfonate, alkali sulfonates such as alkali metal hydroxyethylene alkali metal sulfates; high alkyl naphthalene sulfonates; naphthalene sulfonic acid formalin condensates; sodium laurate, triethanolamine oleate, triethanolamine abie Fatty acid salts such as tate; Polyoxyalkyl ether sulfates; Polyoxye Renkarubon ester sulfates, polyoxyethylene phenyl ether sulfate; dialkyl succinate sulfonate; one or more, such as polyoxyethylene alkyl aryl sulfate salts are preferred.

As the anionic emulsifier, as the reactive emulsifier, a reactive anionic surfactant, a sulfosuccinate-type reactive anionic surfactant, an alkenyl succinate-type reactive anionic surfactant, and the like are preferable. 1 type (s) or 2 or more types can be used.
Commercially available sulfosuccinate-type reactive anionic surfactants include Latemul S-120, S-120A, S-180 and S-180A (all trade names, manufactured by Kao Corporation), Eleminol JS-2 (Products) Name, manufactured by Sanyo Kasei Co., Ltd.). As a commercial item of an alkenyl succinate type reactive anionic surfactant, Latemul ASK (trade name, manufactured by Kao Corporation) and the like can be mentioned.

As the anionic emulsifier, the following surfactants are also suitable as reactive emulsifiers.
Sulfoalkyl (carbon number 1 to 4) ester salt type surfactant of aliphatic unsaturated carboxylic acid having 3 to 5 carbon atoms, for example, 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium (Meth) acrylic acid sulfoalkyl ester salt type surfactants such as salts; sulfopropylmaleic acid alkylester sodium salt, sulfopropylmaleic acid polyoxyethylene alkylester ammonium salt, sulfoethylfumaric acid polyoxyethylene alkylester ammonium salt, etc. Aliphatic unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt surfactants.

Maleic acid dipolyethylene glycol ester alkylphenol ether sulfate, phthalic acid dihydroxyethyl ester (meth) acrylate sulfate, 1-allyloxy-3-alkylphenoxy-2-polyoxyethylene sulfate (trade name: ADEKA Rear soap SE-10N, manufactured by ADEKA), polyoxyethylene alkyl alkenyl phenol sulfate ester (trade name: Aqualon, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SR-10 (EO mole number = 10; manufactured by ADEKA) ), SR-20 (EO mole number = 20; manufactured by ADEKA), SR-30 (EO mole number = 30; manufactured by ADEKA).

Moreover, as a reactive emulsifier, since the stability with respect to a pigment, a filler, etc. is improved according to the addition structure of ethylene oxide, for example, α-hydro-ω- [2- (1-propenyl) -4-nonylphenoxy] Polyoxyethylene (trade name: Aqualon, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like are suitable.

In the emulsion for vibration damping materials (I), as the emulsion (i), a commonly used one may be used, and is not particularly limited. For example, one or more of acrylic copolymers are used. It is preferable that it contains.
Such an acrylic copolymer usually exists in a form dispersed in a medium. That is, the emulsion (i) preferably has a medium and an acrylic copolymer dispersed in the medium. The medium is preferably an aqueous medium, and examples thereof include water and a mixed solvent of water and a solvent mixed with water. Among these, water is preferable in consideration of safety and environmental impact when applying the paint containing the emulsion for vibration damping material (I) of the present invention.

As a content rate of the said acrylic copolymer, it is suitable that it is 70 mass% or less with respect to 100 mass% of total amounts of emulsion (i). If it exceeds 70% by mass, the viscosity of the resulting emulsion for vibration damping material (I) may become too high, and sufficient dispersion stability may not be maintained, which may cause aggregation. More preferably, it is 60 mass% or less.

In the present invention, the “acrylic copolymer” is a copolymer obtained by using at least two types of monomer components, and at least one of the monomer components is an unsaturated double bond. And a monomer having a —COO group (hereinafter also referred to as “(meth) acrylic acid (salt) monomer”). That is, at least one of the monomer components is C (R ¹ ) ₂ = CH-COOR ² or C (R ³ ) ₂ = C (CH ₃ ) -COOR ⁴ (R ¹ , R ² , R ³ And R ⁴ are the same or different and each represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group, or a monomer represented by a linear, branched or cyclic alkyl group. To do.
In addition, when using 2 or more types of acrylic copolymers, these are a weight average molecular weight, a glass transition temperature, SP value (solubility coefficient), the kind of monomer used, the usage rate of a monomer, for example. What is necessary is just to be different in any of various physical properties such as.

In the monomer component, the (meth) acrylic acid (salt) monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, Fumaric acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl Acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate , Cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate , Tridecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, vinyl formate, vinyl acetate, vinyl propionate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diallyl phthalate, triallyl cyanurate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate, etc., and one or more of these salts and esterified products Is preferably used.

The salt is preferably a metal salt, ammonium salt, organic amine salt or the like. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as alkaline earth metal atoms such as calcium and magnesium; aluminum, Trivalent metal atoms such as iron are suitable, and the organic amine salt is preferably an alkanolamine salt such as an ethanolamine salt, diethanolamine salt, or triethanolamine salt, or a triethylamine salt.

As a content rate of the said (meth) acrylic acid (salt) type monomer, it is 30-100 mass% with respect to 100 mass% of all the monomer components used for manufacture of an acrylic copolymer, for example. Is preferred. More preferably, it is 50-100 mass%.

The monomer component may also contain other monomers copolymerizable with the (meth) acrylic acid (salt) monomer. Examples of other monomers include divinylbenzene, styrene, α-methylstyrene, vinyl toluene, ethyl vinyl benzene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, and N-methylol. And methacrylamide.
As a content rate of the said other monomer, it is preferable that it is 70 mass% or less with respect to 100 mass% of all the monomer components, for example, More preferably, it is 50 mass% or less.

As said acrylic copolymer, it is suitable that glass transition temperature (Tg) is -50-60 degreeC. Thereby, it becomes possible to express a higher vibration damping property under a wide temperature range, and the vibration damping property in a practical range of 20 to 60 ° C. becomes better.
In addition, as Tg of an acrylic copolymer, it may be determined based on the knowledge already acquired, and may be controlled by the kind and usage ratio of the monomer component. It can be calculated from a calculation formula.

In the formula, Tg is Tg (absolute temperature) of the acrylic copolymer. W ₁ , W ₂ ,..., W _n are mass fractions of each monomer with respect to all monomer components. T ₁ , T ₂ ,..., T _n are glass transition temperatures (absolute temperatures) of a homopolymer (homopolymer) composed of each monomer component.

When two or more kinds of acrylic copolymers are used as the acrylic copolymer, it is preferable to use those having different Tg. By providing a difference in the glass transition temperature (Tg) in this way, it becomes possible to express higher vibration damping properties under a wide temperature range, and particularly in the practical range of 20 to 60 ° C. Will be greatly improved. When three or more kinds of acrylic copolymers are used, it is sufficient that at least two of these acrylic copolymers have different Tg. For the remaining one or more kinds, the two kinds of acrylic copolymers are used. The same Tg as any of the copolymers may be used.

As an acrylic copolymer having a different Tg, a high Tg is “acrylic copolymer (A)”, and a low Tg is “acrylic copolymer (B)”. Preferably there is. If the difference is less than 15 ° C., there is a possibility that the vibration damping property cannot be sufficiently exhibited at either 20 ° C. or 60 ° C. More preferably, it is 20 degreeC or more, More preferably, it is 25 degreeC or more. Further, if the temperature difference is too large, there is a possibility that the vibration damping property in the practical range may not be sufficient, so the Tg difference is preferably 100 ° C. or less. More preferably, it is 90 degrees C or less, More preferably, it is 80 degrees C or less.

Specifically, the glass transition temperature (TgA) of the acrylic copolymer (A) is preferably 0 ° C. or higher. Thereby, the drying property of the damping material coating film formed using the coating material containing the emulsion for damping material (I) of the present invention is improved, and the expansion and cracks of the coating film surface are sufficiently suppressed. Become. That is, a vibration damping material having extremely excellent vibration damping properties is formed. More preferably, it is 5 ° C. or higher.

The acrylic copolymer preferably has a weight average molecular weight of 20,000 to 250,000. If it is less than 20,000, the vibration damping property may not be sufficient, and the resulting emulsion (I) for vibration damping material may not be excellent in stability when blended in the paint. If it exceeds 250,000, for example, when two or more kinds of acrylic copolymers are used, the compatibility is not sufficient, so that the balance of vibration damping properties cannot be kept sufficiently, particularly in the range of 30 to 40 ° C. There is a possibility that the vibration damping property cannot be improved, and there is a possibility that the film-forming property at a low temperature in the state of being blended in the paint may not be sufficient. Preferably, it is 30000-220,000, More preferably, it is 40000-200000.
The weight average molecular weight can be determined, for example, by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

When two or more kinds of acrylic copolymers are used as the acrylic copolymer, it is also preferable to use those having different weight average molecular weights. Thus, by providing a difference in weight average molecular weight, it becomes possible to express higher vibration damping properties under a wide temperature range. When three or more kinds of acrylic copolymers are used, it is sufficient that at least two of the acrylic copolymers have different weight average molecular weights. The weight average molecular weight may be the same as any of the acrylic copolymers.
Specifically, the difference in weight average molecular weight is preferably 4000 or more. More preferably, it is 10,000 or more. Moreover, it is suitable that it is 200,000 or less.

Although it does not specifically limit as an average particle diameter of the said emulsion (i), For example, it is suitable that it is 10-1000 nm. If the average particle size is less than 10 nm, sufficient pigment dispersibility cannot be exhibited and aggregation may occur, or the mechanical stability may not be sufficiently improved. No more. More preferably, it is 20-500 nm.
In addition, as an average particle diameter (average particle diameter), for example, after diluting an emulsion with distilled water and sufficiently stirring and mixing, about 10 ml is sampled in a glass cell, and this is taken as a dynamic light scattering photometer DLS-700 (Otsuka). It can obtain | require by measuring by an electronic company.

Although it does not specifically limit as pH of the said emulsion (i), For example, it is preferable that it is 2-10, More preferably, it is 3-9. The pH of the emulsion can be adjusted by adding ammonia water, water-soluble amines, alkaline hydroxide aqueous solution, and the like to the emulsion.

Although it does not specifically limit as a viscosity of the said emulsion (i), For example, it is preferable that it is 10-10000 mPa * s, More preferably, it is 50-5000 mPa * s.
The viscosity can be measured using a B-type rotational viscometer under the conditions of 25 ° C. and 20 rpm.

Although it does not specifically limit as a form of the said emulsion (i), For example, it is suitable that it has a core-shell composite structure, a homogeneous structure, or a mixed structure which consists of 2 or more types of emulsion.
Here, the “core-shell composite structure” has a core part made of an acrylic copolymer and a shell part made of an acrylic copolymer different from the acrylic copolymer forming the core part. It means a structure in which two kinds of acrylic copolymers are not completely compatible but formed heterogeneously. In such a core-shell composite structure, the surface of the core part is preferably covered with the shell part. In this case, it is preferable that the surface of the core part is completely covered with the shell part, but it may not be completely covered. For example, the core part may be covered in a mesh shape or in some places. The part may be exposed.
The term “homogeneous structure” means a structure formed from one type of acrylic copolymer, or a structure obtained when two or more types of acrylic copolymers are completely compatible. To do.
Furthermore, the “mixed structure composed of two or more emulsions” means a structure formed by mixing two or more emulsions formed from two or more kinds of acrylic copolymers.

The emulsion (i) having the core-shell composite structure can be obtained by multistage polymerization using a usual emulsion polymerization method. Specifically, after the monomer component is emulsion-polymerized in an aqueous medium in the presence of a surfactant and / or a protective colloid to form a core portion, the monomer component is further added to the emulsion containing the core portion. It is preferably obtained by emulsion polymerization to form a shell portion.
The emulsion (i) having the homogeneous structure can be obtained by one-stage polymerization using a normal emulsion polymerization method. Specifically, it is preferably obtained by emulsion polymerization of a monomer component in an aqueous medium in the presence of a surfactant and / or a protective colloid.
The emulsion (i) having the above-mentioned mixed structure can be obtained by mixing two or more kinds of emulsions by one-stage polymerization using a normal emulsion polymerization method and then mixing them. Specifically, two or more types of emulsions are obtained by emulsion polymerization of monomer components in an aqueous medium in the presence of a surfactant and / or protective colloid, and then obtained by mixing them. It is preferable. In addition, what is necessary is just to perform mixing of 2 or more types of emulsions by a normal method.

Below, the manufacturing method using the said emulsion polymerization is further demonstrated.
In the said manufacturing method, it is as having mentioned above as an aqueous medium and a monomer component.
What is necessary is just to use what is normally used for emulsion polymerization as said surfactant, Although it does not specifically limit, For example, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, It is preferable to use one kind or two or more kinds of polymer surfactants and these reactive surfactants.

It does not specifically limit as said anionic surfactant, For example, the 1 type (s) or 2 or more types of the anionic emulsifier mentioned above can be used.
The nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan aliphatic ester; polyoxyethylene sorbitan aliphatic ester; aliphatic such as monolaurate of glycerol Monoglycerides; polyoxyethyleneoxypropylene copolymers; condensation products of ethylene oxide and aliphatic amines, amides or acids, and the like, and one or more of these can be used.
The cationic surfactant is not particularly limited, and examples thereof include dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, dialkylimidazolinium salts, and the like. Can be used.

The amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropylbetaine, alkylhydroxysulfobetaine, and the like. 1 type (s) or 2 or more types can be used.
The polymer surfactant is not particularly limited. For example, polyvinyl alcohol and modified products thereof; (meth) acrylic acid-based water-soluble polymer; hydroxyethyl (meth) acrylic acid-based water-soluble polymer; hydroxypropyl (meta ) Acrylic acid-based water-soluble polymer; polyvinylpyrrolidone and the like can be mentioned, and one or more of these can be used.

Among the above surfactants, it is preferable to use a non-nonylphenyl type surfactant from the environmental viewpoint.
The amount of the surfactant used may be appropriately set according to the type of surfactant to be used, the type of monomer component, and the like. For example, the monomer used to form the acrylic copolymer It is preferable that it is 0.3-10 weight part with respect to 100 weight part of total amounts of a component, More preferably, it is 0.5-5 weight part.

Examples of the protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt; natural polysaccharides such as guar gum Etc., and one or more of these can be used. The protective colloid may be used alone or in combination with a surfactant.
The use amount of the protective colloid may be appropriately set according to the use conditions and the like, for example, 5 weights with respect to 100 parts by weight of the total amount of monomer components used to form the acrylic copolymer. The amount is preferably at most 3 parts by weight, more preferably at most 3 parts by weight.

In the above production method, it is preferable to use a polymerization initiator in order to initiate emulsion polymerization. The polymerization initiator is not particularly limited as long as it is a substance that decomposes by heat and generates radical molecules, but a water-soluble initiator is preferably used. For example, persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; water-soluble azo such as 2,2-azobis (2-amidinopropane) dihydrochloride, 4,4-azobis (4-cyanopentanoic acid) Compounds: Thermal decomposition initiators such as hydrogen peroxide; Hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and Rongalite, potassium persulfate and metal salts, redox polymerization initiators such as ammonium persulfate and sodium bisulfite, etc. And one or more of these can be used.
The amount of the polymerization initiator used is not particularly limited and may be set as appropriate according to the type of the polymerization initiator. For example, the total amount of monomer components used to form the acrylic copolymer is 100. It is preferable that it is 0.1-2 weight part with respect to a weight part, More preferably, it is 0.2-1 weight part.

In order to promote emulsion polymerization, the polymerization initiator can be used in combination with a reducing agent as necessary. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; for example, reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. These 1 type (s) or 2 or more types can be used.
It does not specifically limit as the usage-amount of the said reducing agent, For example, it is 0.05-1 weight part with respect to 100 weight part of total amounts of the monomer component used in forming an acrylic copolymer. preferable.

In the above production method, it is also preferable to use a chain transfer agent at the time of emulsion polymerization, if necessary, in order to adjust the weight average molecular weight of the acrylic copolymer. The chain transfer agent may be a commonly used one, and is not particularly limited. For example, hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan Alkyl mercaptans such as carbon tetrachloride, carbon tetrabromide, halogenated hydrocarbons such as ethylene bromide; mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopyropionate tridecyl Mercaptocarboxylic acid alkyl esters such as esters; mercaptocarboxylic acid alkoxyalkyl esters such as mercaptoacetic acid methoxybutyl ester and mercaptopropionic acid methoxybutyl ester; octanoic acid 2-mercaptoethyl esters Carboxylic acid mercaptoalkyl esters such as Le; alpha-methylstyrene dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, dipentene, anisole, one allyl alcohol or 2 or more are preferable. Among these, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan are preferably used.
The amount of the chain transfer agent used is not particularly limited. For example, it is preferably 2 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components used to form the acrylic copolymer. More preferably, it is 1.0 part by weight or less.

Regarding the emulsion polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is preferably 0 to 100 ° C., and more preferably 40 to 95 ° C., for example. Further, the polymerization time is not particularly limited, and for example, 1 to 15 hours is preferable.
Moreover, it does not specifically limit as addition methods, such as a monomer component and a polymerization initiator, For example, methods, such as a batch addition method, a continuous addition method, a multistage addition method, are applicable. Moreover, you may combine these addition methods suitably.

The emulsion for vibration damping material (I) of the present invention can be obtained by adding an anionic emulsifier to the emulsion (i), but the addition time is not particularly limited, and before the emulsion (i) is produced, It may be either during production or after production. Moreover, it is good also as adding in two or more steps among three steps before manufacture, the middle of manufacture, and after manufacture. Among them, it is preferable to add an anionic emulsifier at least at the end of the production process of the emulsion (i), whereby the particle size of the emulsion for vibration damping material (I) can be made uniform, that is, new particles Is not generated, the emulsion for vibration damping material (I) can be made excellent in mechanical stability and pigment dispersibility, and the drying property and vibration damping property can be further improved.
Here, “the final stage of the production process of the emulsion (i)” means a time point when an emulsion having an average particle diameter of 10 to 1000 nm is obtained. Preferably, it is the time when an emulsion of 20 to 500 nm is obtained.

A chain transfer agent is preferably used as the damping material emulsion.
Examples of the chain transfer agent include alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan; carbon tetrachloride, carbon tetrabromide Halogenated hydrocarbons such as ethylene bromide; mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopropionic acid tridecyl ester, etc. mercaptocarboxylic acid alkyl ester; mercaptoacetic acid methoxybutyl ester , Mercaptocarboxylic acid alkoxyalkyl esters such as mercaptopropionic acid methoxybutyl ester; carboxylic acid mercaptoalkyl esters such as octameric acid 2-mercaptoethyl ester; α- Chill dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, dipentene, anisole, one allyl alcohol or 2 or more are preferable. Among these, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan are preferably used.

The present invention is also a vibration damping composition comprising the above vibration damping emulsion.
The emulsion for damping material of the present invention can constitute a damping material blend together with other components as necessary. Such a damping material composition essentially including the emulsion for damping material of the present invention is one of the preferred embodiments of the present invention, and is an aqueous system capable of exhibiting excellent heat drying properties and damping properties. A vibrating material can be formed. The use method of the emulsion for damping materials which uses the said damping material composition as a water-system damping material is also one of the preferable forms of this invention.
As the vibration damping composition, for example, the solid content is preferably 40 to 90% by mass, more preferably 50 to 83% by mass with respect to 100% by mass of the total amount of the vibration damping composition. %, More preferably, it is 60-80 mass%. Moreover, it is preferable to set pH of a damping material compound to 7-11, More preferably, it is 7-9.
The blending amount of the damping material emulsion (I) in the damping material composition is, for example, that the damping material emulsion (I) has a solid content of 10% with respect to 100% by mass of the damping material composition. It is preferable to set it to be ˜60 mass%, more preferably 15 to 55 mass%.

Examples of the other components include, for example, a solvent, a plasticizer, a stabilizer, a thickener, a wetting agent, an antiseptic agent, an antifoaming agent, a filler, a colorant, a dispersant, a rust preventive pigment, an antifoaming agent, and aging. One or more of an inhibitor, an antifungal agent, an ultraviolet absorber, an antistatic agent and the like can be used. Among these, it is preferable to include a filler. Further, it is also suitable to contain a pigment (colorant or rust preventive pigment), and the vibration damping composition containing the emulsion for vibration damping material (I) of the present invention is particularly excellent in pigment dispersibility. By including the pigment, this effect can be sufficiently exhibited.
In addition, said other component can be mixed with the said emulsion (I) for damping materials etc. using a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver etc., for example.

Although the said other component should just use a normal thing and is not specifically limited, For example, the following compound etc. can be used.
Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and the like. What is necessary is just to set suitably as a compounding quantity of a solvent, for example so that the solid content concentration of emulsion (I) for damping materials in a damping material formulation may become the range mentioned above.

Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. As a compounding quantity of a thickener, it is preferable to set it as 0.01-2 weight part with solid content with respect to 100 weight part of solid content of emulsion (I) for damping materials, for example, More preferably, it is 0.00. 05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight.
Examples of the filler include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide, glass talk, magnesium carbonate, aluminum hydroxide, talc, diatomaceous earth, and clay; Examples of the inorganic filler include glass flakes and mica; and fibrous inorganic fillers such as metal oxide whiskers and glass fibers. As a compounding quantity of an inorganic filler, it is preferable to set it as 50-700 weight part with respect to 100 weight part of solid content of the emulsion (I) for vibration damping materials, for example, More preferably, it is 100-550 weight part. .

Examples of the colorant include organic or inorganic colorants such as titanium oxide, carbon black, dial, hansa yellow, benzine yellow, phthalocyanine blue, and quinacridone red.
Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
Examples of the rust preventive pigment include a metal phosphate, a metal molybdate, and a metal borate.
Examples of the antifoaming agent include silicon-based antifoaming agents.

As the other component, it is preferable to use a foaming agent. In this case, as described later, it is preferable to heat-dry the vibration damping composition to form a vibration damping coating film. By further adding a foaming agent to the emulsion for damping material (I), formation of a uniform foamed structure of the damping material and an increase in the thickness of the film are achieved, resulting in sufficient heat drying and high damping. Tremor will be developed. Thus, the damping material composition comprising the damping material emulsion (I) of the present invention and the foaming agent is also one of the preferred embodiments of the present invention. In addition, other components may be further included as necessary.

The foaming agent is not particularly limited, and for example, a low-boiling hydrocarbon encapsulated heated expansion capsule, an organic foaming agent, an inorganic foaming agent, and the like are suitable, and one or more of these can be used. Examples of the heated expansion capsule include Matsumoto Microsphere F-30, F-50 (manufactured by Matsumoto Yushi Co., Ltd.); EXPANSELL WU642, WU551, WU461, DU551, DU401 (manufactured by Nippon Expandcel). Examples of the organic blowing agent include azodicarbonamide, azobisisobutyronitrile, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazine, p-oxybis (benzenesulfohydrazide)), N, N- Examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, and silicon hydride.
As a compounding quantity of the said foaming agent, it is preferable to set it as 0.5-5.0 weight part with respect to 100 weight part of emulsions (I) for damping materials, More preferably, it is 1.0-3. 0 parts by weight.

It is preferable that the vibration damping composition further comprising a foaming agent further comprises an inorganic pigment, thereby more sufficiently exhibiting heat drying properties and high vibration damping properties as described above. It becomes possible to confirm.
It does not specifically limit as said inorganic pigment, For example, 1 type (s) or 2 or more types, such as the inorganic coloring agent mentioned above and an inorganic rust preventive pigment, can be used.
As a compounding quantity of the said inorganic pigment, it is preferable to set it as 50-700 weight part with respect to 100 weight part of emulsions (I) for damping materials, More preferably, it is 100-550 weight part.

As the other component, a polyvalent metal compound may be further used. In this case, the polyvalent metal compound improves the stability, dispersibility, heat drying property, and damping property of the damping material formed from the damping material formulation. It does not specifically limit as a polyvalent metal compound, For example, zinc oxide, zinc chloride, zinc sulfate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The form of the polyvalent metal compound is not particularly limited, and may be, for example, a powder, an aqueous dispersion, an emulsion dispersion, or the like. Especially, since the dispersibility in a damping material formulation improves, it is preferable to use it with the form of an aqueous dispersion or an emulsion dispersion, More preferably, it is used with the form of an emulsion dispersion. Moreover, the usage-amount of a polyvalent metal compound becomes like this. Preferably it is 0.05-5.0 weight part with respect to 100 weight part of solid content in a damping material compound, More preferably, 0.05-3. 5 parts by weight.

The said damping material composition forms the coating film used as a damping material, for example by apply | coating to a base material and drying. The substrate is not particularly limited. Moreover, as a method of apply | coating a damping material compound to a base material, it can apply | coat using a brush, a spatula, an air spray, an airless spray, a mortar gun, a lysing gun etc., for example.
The coating amount of the vibration damping composition may be appropriately set depending on the application, desired performance, etc. For example, the surface weight of the coating film at the time of drying (after) is 1.0 to 7.0 kg / m ² . Preferably, it is 2.0 to 6.0 kg / m ² . In addition, by using the vibration damping composition of the present invention, it is possible to obtain a coating film that hardly causes expansion and cracks during drying and that does not easily cause sagging of a vertical surface. The coating method of the damping material composition which is applied so that the surface weight of the coated film after drying is 2.0 to 6.0 kg / m ² and is dried is also one of the preferred embodiments of the present invention. is there. Moreover, the damping material obtained by the coating method of the damping material composition is also one of the preferred embodiments of the present invention.
As the vibration damping composition, for example, the solid content is preferably 40 to 90% by mass, more preferably 50 to 83% by mass with respect to 100% by mass of the total amount of the vibration damping composition. %, More preferably, it is 60-80 mass%. Moreover, it is preferable to set pH of a damping material compound to 7-11, More preferably, it is 7-9.
As a compounding quantity of the emulsion for damping materials in the said damping material composition, the solid content of the emulsion for damping materials will be 10-60 mass% with respect to 100 mass% of solid content of a damping material composition, for example. It is preferable to set as described above, and more preferably 15 to 55% by mass.

Examples of the other components include a solvent; an aqueous cross-linking agent; a plasticizer; a stabilizer; a thickener; a wetting agent; an antiseptic; an antifoaming agent; a filler; 1 type or 2 types or more, such as anti-aging agent; antifungal agent; ultraviolet absorber; antistatic agent can be used. Among these, it is preferable to include a filler. In addition, the said other component can be mixed with the said emulsion for vibration damping materials etc. using a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver etc., for example.

Although the said other component should just use a normal thing and is not specifically limited, For example, the following compound etc. can be used.
Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and the like. What is necessary is just to set suitably as the compounding quantity of a solvent so that the solid content density | concentration of the emulsion for damping materials in a damping material formulation may become the range mentioned above, for example.

Examples of the aqueous crosslinking agent include oxazoline compounds such as Epocross WS-500, WS-700, K-2010, 2020, 2030 (all trade names, manufactured by Nippon Shokubai Co., Ltd.); Adeka Resin EMN-26-60, EM- Epoxy compounds such as 101-50 (both trade names, manufactured by ADEKA); Melamine compounds such as Cymel C-325 (trade names, manufactured by Mitsui Cytec); Block isocyanate compounds; AZO-50 (trade names, 50 Zinc oxide compounds such as a mass% zinc oxide aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd.) are suitable. As a compounding quantity of a water-system crosslinking agent, it is preferable to set it as 0.01-20 weight part by solid content with respect to 100 weight part of solid content of the emulsion for damping materials, More preferably, it is 0.15-15. Part by weight, more preferably 0.5 to 15 parts by weight, which may be added to the emulsion for vibration damping materials, or may be added simultaneously when other components are blended as a vibration damping material blend.
By mixing a crosslinking agent with the emulsion or composition for vibration damping material, the toughness of the resin is improved, and as a result, sufficient high vibration damping properties are exhibited in a high temperature region. Among them, it is preferable to use an oxazoline compound.

Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. As a compounding quantity of a thickener, it is preferable to set it as 0.01-2 weight part with solid content with respect to 100 weight part of solid content of the emulsion for vibration damping materials, for example, More preferably, 0.05-1 0.5 parts by weight, more preferably 0.1 to 1 part by weight.
Examples of the filler include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide, glass talk, magnesium carbonate, aluminum hydroxide, talc, diatomaceous earth, and clay; Examples of the inorganic filler include glass flakes and mica; and fibrous inorganic fillers such as metal oxide whiskers and glass fibers. As a compounding quantity of an inorganic filler, it is preferable to set it as 50-700 weight part with respect to 100 weight part of solid content of the emulsion for vibration damping materials, for example, More preferably, it is 100-550 weight part.

Examples of the colorant include organic or inorganic colorants such as titanium oxide, carbon black, dial, hansa yellow, benzine yellow, phthalocyanine blue, and quinacridone red.
Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
Examples of the rust preventive pigment include a metal phosphate, a metal molybdate, and a metal borate.
Examples of the antifoaming agent include silicon-based antifoaming agents.

As the other component, a foaming agent may be used. In this case, as described later, it is preferable to heat-dry the vibration damping composition to form a vibration damping coating film. By mixing a foaming agent with the above-mentioned emulsion for vibration damping materials, the formation of a uniform foamed structure of the vibration damping material and thickening of the film, etc., resulting in sufficient heat drying and high vibration damping Will be. Thus, the damping material composition comprising the damping material emulsion and the foaming agent of the present invention is also one of the preferred embodiments of the present invention.
In addition, such a damping material composition may contain other components as necessary.

The foaming agent is not particularly limited, and for example, a low-boiling hydrocarbon encapsulated heated expansion capsule, an organic foaming agent, an inorganic foaming agent, and the like are suitable, and one or more of these can be used. Examples of the heated expansion capsule include Matsumoto Microsphere F-30, F-50 (manufactured by Matsumoto Yushi Co., Ltd.); EXPANSELL WU642, WU551, WU461, DU551, DU401 (manufactured by Nippon Expandcel). Examples of the organic foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazine, p-oxybis (benzenesulfohydrazide), and the like. Examples of the foaming agent include sodium bicarbonate, ammonium carbonate, silicon hydride and the like.
As a compounding quantity of the said foaming agent, it is preferable to set it as 0.5-5.0 weight part with respect to 100 weight part of emulsions for damping materials, for example, More preferably, it is 1.0-3.0 weight part It is.

It is preferable that the vibration damping composition comprising the emulsion for vibration damping material and the foaming agent further comprises an inorganic pigment, whereby heat drying properties and high vibration damping properties as described above can be obtained. It becomes possible to confirm the expression sufficiently.
It does not specifically limit as said inorganic pigment, For example, 1 type (s) or 2 or more types, such as the inorganic coloring agent mentioned above and an inorganic rust preventive pigment, can be used.
As a compounding quantity of the said inorganic pigment, it is preferable to set it as 50-700 weight part with respect to 100 weight part of emulsion for damping materials, for example, More preferably, it is 100-550 weight part.

As the other component, a polyvalent metal compound may be further used. In this case, the polyvalent metal compound improves the stability, dispersibility, heat drying property, and damping property of the damping material formed from the damping material formulation. It does not specifically limit as a polyvalent metal compound, For example, zinc oxide, zinc chloride, zinc sulfate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The form of the polyvalent metal compound is not particularly limited, and may be, for example, a powder, an aqueous dispersion, an emulsion dispersion, or the like. Especially, since the dispersibility in a damping material formulation improves, it is preferable to use it with the form of an aqueous dispersion or an emulsion dispersion, More preferably, it is used with the form of an emulsion dispersion. Moreover, the usage-amount of a polyvalent metal compound becomes like this. Preferably it is 0.05-5.0 weight part with respect to 100 weight part of solid content in a damping material compound, More preferably, 0.05-3. 5 parts by weight.

The conditions for applying the vibration damping composition and drying to form a coating film may be, for example, heat drying or room temperature drying, but heat drying from the viewpoint of efficiency. In the present invention, it is preferable because of excellent heat drying property. As temperature of heat drying, it is preferable to set it as 80-210, for example, More preferably, it is 110-180 degreeC, More preferably, it is 120-170 degreeC.

Although it does not specifically limit as a use of the damping material compound containing the emulsion (I) for damping materials of this invention, Since it can exhibit the outstanding heat drying property, damping property, etc., for example, the interior of a car In addition to under the floor, the present invention can be suitably applied to railway vehicles, ships, aircraft, electrical equipment, building structures, construction equipment, and the like.

The emulsion for vibration damping material (I) of the present invention has the above-described structure, and is excellent in vibration damping properties, drying properties and stability in a wide temperature range, and improves the coating surface of the coating film. Therefore, it is particularly useful as a material used for vibration damping materials of various structures.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
In the following examples and the like, the weight average molecular weight (Mw), glass transition temperature (Tg) and viscosity were determined as described above. Moreover, film cloudiness and SP value were calculated | required as follows.
(Film cloudiness)
The obtained emulsion was poured into a mold of 100.0 mm (length) x 50.0 mm (width) x 2.00 mm (height), left at room temperature for 10 minutes, and then baked at 140 ° C. The transparency of the resin film was confirmed visually.

(SP value)
It was determined by the following Small formula. In the formula, δ is the SP value of the acrylic copolymer. Δe ₁ is a calculated value (kcal / mol) of evaporation energy of each monomer component constituting the acrylic copolymer, and ΣΔe ₁ is a calculated value of all monomer components constituting the acrylic copolymer. Is the sum of ΔV _m is a calculated value (ml / mol) of each monomer component constituting the acrylic copolymer, and ΣΔV _m is a calculated value of all monomer components constituting the acrylic copolymer. Is the sum of x is the molar distribution of each component of the monomer constituting the acrylic copolymer.

<Emulsion for damping material>
Example 1
Deionized water (37.7 parts) was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. Meanwhile, in a dropping funnel, methyl methacrylate (14.6 parts), styrene (33.6 parts), 2-ethylhexyl acrylate (22.5 parts), butyl acrylate (25.3 parts), acrylic acid (1.0 parts) ), Methacrylic acid (3.0 parts), anionic emulsifier A (polyoxyethylene alkyl ether sulfate ester salt prepared beforehand in a 20% aqueous solution; trade name “Hytenol NF-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (2 parts in terms of solid content with respect to 100 parts of all monomer components) and deionized water (10 parts) were charged to prepare a monomer emulsion.
Next, the reaction is started by dropping the obtained monomer emulsion into a polymerizer adjusted to 70 ° C., and after raising the temperature to 75 ° C., the monomer is maintained while maintaining the internal temperature at 75 ° C. The emulsion was uniformly dropped over 3 hours, and at the same time, a 5% aqueous potassium persulfate solution (7.0 parts) and a 2% aqueous sodium hydrogen sulfite solution (17.5 parts) were uniformly added dropwise over 3 hours, An emulsion was formed. After completion of the dropping, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer component. Thereafter, the mixture was cooled to 25 ° C. and an appropriate amount of 25% aqueous ammonia was added thereto, thereby obtaining an emulsion (1). The obtained emulsion was made into the emulsion for vibration damping materials.
About the obtained emulsion for damping materials, solid content concentration, pH, and viscosity were calculated | required. The results are shown in Table 1.

Example 2
A damping material emulsion was obtained in the same manner as in Example 1 except that 1.5 parts of a foaming agent ("Expansel WU642", manufactured by Nippon Philite Co., Ltd.) was further added to 100 parts of the emulsion.
About this damping material emulsion, the solid content concentration, pH and viscosity were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Deionized water (37.7 parts) was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. Meanwhile, in a dropping funnel, methyl methacrylate (14.6 parts), styrene (33.6 parts), 2-ethylhexyl acrylate (22.5 parts), butyl acrylate (25.3 parts), acrylic acid (1.0 parts) ), Methacrylic acid (3.0 parts), anionic emulsifier A (polyoxyethylene alkyl ether sulfate ester salt prepared beforehand in a 20% aqueous solution; trade name “Hytenol NF-08”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (2 parts in terms of solid content with respect to 100 parts of all monomer components) and deionized water (10 parts) were charged to prepare a monomer emulsion.
Next, the reaction is started by dropping the obtained monomer emulsion into a polymerizer adjusted to 70 ° C., and after raising the temperature to 75 ° C., the monomer is maintained while maintaining the internal temperature at 75 ° C. The emulsion was uniformly dropped over 3 hours, and at the same time, a 5% aqueous potassium persulfate solution (7.0 parts) and a 2% aqueous sodium hydrogen sulfite solution (17.5 parts) were uniformly added dropwise over 3 hours, An emulsion was formed. After completion of the dropping, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer component. Thereafter, the mixture was cooled to 25 ° C. and an appropriate amount of 25% aqueous ammonia was added thereto, thereby obtaining an emulsion (1).
In the obtained emulsion (1), 1 part of an anionic emulsifier B (trade name “Latemul E-118B”, manufactured by Kao Corporation, based on 100 parts of all monomer components used to obtain the emulsion (1). ) Was added and mixed to obtain an emulsion for vibration damping materials.
About the obtained emulsion for damping materials, solid content concentration, pH, and viscosity were calculated | required. The results are shown in Table 1.

Examples 4-8, Comparative Example 1
A damping material emulsion was obtained in the same manner as in Example 1 except that the composition of the monomer component, the type of anionic emulsifier, and the amount of the anionic emulsifier were changed to the compositions shown in Table 1.
About each of this emulsion for damping materials, solid content concentration, pH, and viscosity were evaluated similarly to Example 1. The results are shown in Table 1.

Example 9, Comparative Example 2
The composition of the monomer component, the type of anionic emulsifier and the amount of its use were changed to the composition shown in Table 1, and the foaming agent ("Expancel WU642", Nippon Philite Co., Ltd.) with respect to 100 parts of the emulsion. (Product made) Except having added 1.5 parts, it carried out similarly to Example 1, and obtained the emulsion for damping materials.
About each of this emulsion for damping materials, solid content concentration, pH, and viscosity were evaluated similarly to Example 1. The results are shown in Table 1.

Examples 10-12
A damping material emulsion was obtained in the same manner as in Example 1 except that the composition of the monomer component, the type of the anionic emulsifier and the composition of the amount used were changed to those shown in Table 1.
About each of this emulsion for damping materials, solid content concentration, pH, and viscosity were evaluated similarly to Example 1. The results are shown in Table 1.

In Table 1, the emulsifier A used is Hitenol NF-08, an emulsifier for polymerization, the emulsifier B is a post-added anionic emulsifier Latemul E-118B, and the used emulsifier C is a post-added anionic emulsifier Plex SS-H. The emulsifier D used is a post-added anionic emulsifier Neucor 707SF. The emulsifiers A to D used in Table 2 are also the same.

Example 13
Deionized water (76 parts) was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. Meanwhile, in a dropping funnel, methyl methacrylate (24.3 parts), styrene (40.0 parts), 2-ethylhexyl acrylate (22.5 parts), butyl acrylate (12.2 parts), acrylic acid (1.0 parts) ), T-dodecyl mercaptan (0.8 parts), sulfate ester salt of polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol NF-08”, 10 parts) previously adjusted to a 20% aqueous solution, and Monomer emulsion 1 consisting of deionized water (10 parts) was charged.
The reaction is started by dropping the monomer emulsion 1 into a polymerization vessel adjusted to 70 ° C., and after raising the temperature to 80 ° C., the monomer emulsion 1 is kept for 2 hours while maintaining the internal temperature at 80 ° C. The solution was dripped uniformly. At the same time, a 5% aqueous potassium persulfate solution (7 parts) and a 2% aqueous sodium hydrogensulfite solution (17.5 parts) were uniformly added dropwise over 2 hours. The core part emulsion was formed by these dripping. After completion of the dropping, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer component.
The weight average molecular weight and SP value of the core emulsion thus obtained were determined. Moreover, the glass transition temperature was calculated | required from the monomer composition which comprises a core part. These results are shown in Table 2.

Next, in another dropping funnel, methyl methacrylate (27.4 parts), styrene (10.0 parts), 2-ethylhexyl acrylate (29.2 parts), butyl acrylate (32.5 parts), acrylic acid (1. 0 part), t-dodecyl mercaptan (0.6 part), sulfate ester salt of polyoxyethylene alkyl ether prepared beforehand in a 20% aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol NF-08”, 10 parts) And monomer emulsion 2 consisting of deionized water (10 parts) was prepared.
Reaction was started by dripping the prepared monomer emulsion 2 to the emulsion of a core part, and the monomer emulsion 2 was dripped over 2 hours, maintaining internal temperature at 80 degreeC. At the same time, a 5% aqueous potassium persulfate solution (7 parts) and a 2% aqueous sodium hydrogensulfite solution (17.5 parts) were uniformly added dropwise over 2 hours. By these droppings, a shell portion was formed to obtain core-shell type particles. After completion of the dropwise addition, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer. Thereafter, the reaction solution was cooled to 25 ° C. and an appropriate amount of 25% ammonia water was added to obtain an aqueous emulsion (13). About this emulsion (13), SP value of the shell part was calculated | required and the glass transition temperature was calculated | required from the monomer composition which comprises a shell part. The obtained emulsion was made into the emulsion for vibration damping materials.
About the obtained emulsion for vibration damping materials, the weight average molecular weight (total molecular weight), solid content concentration, pH, and viscosity were determined, and the film turbidity was visually evaluated. These results are shown in Table 2.

Example 14
The composition of the monomer component used for the formation of the core part and the shell part was changed to the composition shown in Table 2, and a foaming agent (“Expanse” was further added to 100 parts of the emulsion containing the core-shell type particles. A emulsion for vibration damping materials was obtained in the same manner as in Example 13 except that 1.5 parts of “Cell WU642” (manufactured by Nippon Philite Co., Ltd.) were added.
Various physical properties and the like of this emulsion for vibration damping materials were evaluated in the same manner as in Example 13. The results are shown in Table 2.

Example 15
Deionized water (76 parts) was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. Meanwhile, in a dropping funnel, methyl methacrylate (24.3 parts), styrene (40.0 parts), 2-ethylhexyl acrylate (22.5 parts), butyl acrylate (12.2 parts), acrylic acid (1.0 parts) ), T-dodecyl mercaptan (0.8 parts), sulfate ester salt of polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol NF-08”, 10 parts) previously adjusted to a 20% aqueous solution, and Monomer emulsion 1 consisting of deionized water (10 parts) was charged.
The reaction is started by dropping the monomer emulsion 1 into a polymerization vessel adjusted to 70 ° C., and after raising the temperature to 80 ° C., the monomer emulsion 1 is kept for 2 hours while maintaining the internal temperature at 80 ° C. The solution was dripped uniformly. At the same time, a 5% aqueous potassium persulfate solution (7 parts) and a 2% aqueous sodium hydrogensulfite solution (17.5 parts) were uniformly added dropwise over 2 hours. The core part emulsion was formed by these dripping. After completion of the dropping, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer component.
The weight average molecular weight and SP value of the core emulsion thus obtained were determined. Moreover, the glass transition temperature was calculated | required from the monomer composition which comprises a core part. These results are shown in Table 2.

Next, in another dropping funnel, methyl methacrylate (27.4 parts), styrene (10.0 parts), 2-ethylhexyl acrylate (29.2 parts), butyl acrylate (32.5 parts), acrylic acid (1. 0 part), t-dodecyl mercaptan (0.6 part), sulfate ester salt of polyoxyethylene alkyl ether prepared beforehand in a 20% aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., “Hitenol NF-08”, 10 parts) And monomer emulsion 2 consisting of deionized water (10 parts) was prepared.
Reaction was started by dripping the prepared monomer emulsion 2 to the emulsion of a core part, and the monomer emulsion 2 was dripped over 2 hours, maintaining internal temperature at 80 degreeC. At the same time, a 5% aqueous potassium persulfate solution (7 parts) and a 2% aqueous sodium hydrogensulfite solution (17.5 parts) were uniformly added dropwise over 2 hours. By these droppings, a shell portion was formed to obtain core-shell type particles. After completion of the dropwise addition, the reaction was continued at 75 ° C. for 1 hour to completely consume each monomer. Thereafter, the reaction solution was cooled to 25 ° C. and an appropriate amount of 25% aqueous ammonia was added to obtain an aqueous emulsion (15). About this emulsion (15), SP value of the shell part was calculated | required and the glass transition temperature was calculated | required from the monomer composition which comprises a shell part.

To the emulsion (15), 1 part of an anionic emulsifier (trade name “Latemul E-118B”, manufactured by Kao Corporation) is added to and mixed with 100 parts of all monomer components used to obtain the emulsion (15). By doing so, an emulsion for a vibration damping material was obtained.
About the obtained emulsion for vibration damping materials, the weight average molecular weight (total molecular weight), solid content concentration, pH, and viscosity were determined, and the film turbidity was visually evaluated. These results are shown in Table 2.

Examples 16 and 17, Comparative Examples 3 and 4
The composition of the monomer component used for forming the core part and the shell part was changed to the composition shown in Table 2, and in Example 16 and Comparative Example 4, 100 parts of the emulsion containing core-shell type particles was added. On the other hand, an emulsion for vibration damping materials was obtained in the same manner as in Example 15 except that 1.5 parts of a foaming agent (“Expancel WU642”, manufactured by Nippon Philite) was added.
Various physical properties and the like of this emulsion for vibration damping materials were evaluated in the same manner as in Example 15. The results are shown in Table 2.

The descriptions in Tables 1 and 2 are as follows.
Anionic emulsifier A: Emulsifier for polymerization, “Hytenol NF-08” (trade name, Daiichi Kogyo Seiyaku Co., Ltd.)
Anionic emulsifier B: Post-added anionic emulsifier, “Latemul E-118B” (trade name, Kao Corporation)
Anionic emulsifier C: Post-added anionic emulsifier, “Perex SS-H” (trade name, Kao)
MMA: methyl methacrylate St: styrene 2EHA: 2-ethylhexyl acrylate BA: butyl acrylate AA: acrylic acid MAA: methacrylic acid t-DM: t-dodecyl mercaptan TgA / TgB (° C.): glass transition temperature of core part (A) ( ° C) / Glass transition temperature of shell part (B) (° C)
WA / WB ratio: Mass ratio of core part (A) and shell part (B) (% /%)
ΔSP (BA): A value obtained by subtracting the SP value of the core part (A) from the SP value of the shell part (B). It should be noted that the smaller the ΔSP (BA), the relatively better the compatibility. Conversely, as ΔSP (B−A) is larger, the compatibility is relatively poor.

<Damping material compound>
The emulsions for vibration damping materials obtained in Examples 1 to 17 and Comparative Examples 1 to 4 were blended as follows, and the heat drying property and mechanical stability were evaluated as the vibration damping composition. The results are shown in Tables 1 and 2.
-Damping material emulsion obtained in Examples 1-7 and Comparative Examples 1-2: 100 parts-Calcium carbonate ("NN # 200", manufactured by Nitto Flour Industry Co., Ltd., filler): 250 parts-Dispersant (“Demol EP”, manufactured by Kao Corporation, special polycarbonate / rubonic acid type polymer surfactant): 1 part thickener (“Acryset AT-2”, manufactured by Nippon Shokubai Co., Ltd., alkali-soluble acrylic thickener Agent): 2 parts Antifoaming agent ("Nopco 8034L", manufactured by San Nopco, antifoaming agent, main component: hydrophobic silicone + mineral oil): 0.3 parts

(Heat drying)
The above damping material composition is poured onto a cold rolled steel sheet (SPCC · 15 width × 250 length × thickness 0.8 mm) into molds having thicknesses of 1.5 mm, 4.0 mm and 6.0 mm, and 150 ° C. X Dried for 30 minutes. After drying, the state of the coating film was observed, and the drying property was evaluated according to the following criteria.
Further, based on Examples 5 and 9, the above damping material composition was applied to a cold-rolled steel plate (SPCC · 15 width × 250 length × thickness 0.8 mm) and the surface weight after drying the coating was 1.0 to 7. After coating to 5 kg / m ² , it was dried at 150 ° C. for 30 minutes. After drying, the state of the coating film was observed, and the drying property was evaluated according to the following criteria. The results are shown in Table 3. As a result of the evaluation, the surface weight was smaller and the thinner the film, the better the heat drying property. Moreover, in Example 9, since the foaming agent was contained, even if the surface weight was 6.0 kg / m < ² >, it resulted in exhibiting the outstanding heat drying property.
◯: No blistering △: Several blisters were confirmed on the surface ×: Many blisters were generated on the coating film surface, and there was a large dome-shaped blister

(Machine stability)
After adding 30 g of pure water to 100 g of the above damping material composition, sufficiently stirring and mixing, and filtering through a 100 mesh wire netting, 70 g of the mixture was measured with a Malone test stability tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.). A mechanical stability test was conducted (according to JIS K6828: 1996, scale of scale only 10 kg, disk rotation speed 1000 rpm, rotation time 5 minutes, test temperature 25 ° C.). After the test, the vibration damping composition was filtered through a 100 mesh wire net and dried in a 110 ° C. drying oven for 1 hour. Evaluation after the test was performed by the following formula.
Aggregation rate (%) = (weight of wire mesh after drying (g) −weight of wire mesh before drying (g)) / 50 g × 100
A: Less than 0.1% ○: 0.1% or more to less than 0.5% Δ: 0.5% or more to less than 1.0% x: 1.0% or more

Claims (8)

An emulsion for a damping material comprising an emulsion produced using an anionic emulsifier,
The anionic emulsifier is at least one selected from the group consisting of polyoxyethylene alkyl ether sulfates, alkyl diphenyl ether disulfonates and alkenyl succinates,
The amount of the anionic emulsifier in the total 100 parts by weight of the monomer component used in the preparation of the emulsion, it der than 1.0 part by weight,
The damping material emulsion further comprises at least one free anionic emulsifier selected from the group consisting of polyoxyethylene alkyl ether sulfate ester, alkyl diphenyl ether disulfonate and alkenyl succinic acid di-salt. ,
The vibration control system is characterized in that the content of the free anionic emulsifier is 1.0 part by weight or more with respect to 100 parts by weight of the total amount of monomer components used in the production of the emulsion. Emulsion for materials. The anionic emulsifier is at least one selected from the group consisting of a polyoxyethylene alkyl ether sulfate salt to which an ethylene oxide chain having 7 or more units is added and an alkyl diphenyl ether disulfonate. The emulsion for vibration damping materials according to claim 1, wherein A damping material composition comprising the emulsion for damping material according to claim 1 or 2 . The said damping material mixture contains 1.0-3.0 weight part of foaming agents with respect to 100 weight part of emulsion for damping material which a damping material composition contains. Damping material compound. The damping material composition according to claim 3 or 4, wherein the damping material composition contains an aqueous crosslinking agent. A method of using an emulsion for vibration damping materials, wherein the vibration damping composition according to any one of claims 3 to 5 is used as an aqueous vibration damping material. A method for applying the vibration damping composition according to any one of claims 3 to 5 ,
The coating method is a coating method of a damping material composition, wherein the coating is dried so that the surface weight of the coating film after drying is 2.0 to 6.0 kg / m ² and dried. A vibration damping material obtained by the coating method of the vibration damping composition according to claim 7 .